US8691994B2 - Multi-component polymerization inhibitors for ethylenically unsaturated monomers - Google Patents

Multi-component polymerization inhibitors for ethylenically unsaturated monomers Download PDF

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US8691994B2
US8691994B2 US13/020,487 US201113020487A US8691994B2 US 8691994 B2 US8691994 B2 US 8691994B2 US 201113020487 A US201113020487 A US 201113020487A US 8691994 B2 US8691994 B2 US 8691994B2
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nitroxide
polymerization
ethylenically unsaturated
hydroxylamine
composition
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US20120203020A1 (en
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David Youdong Tong
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Ecolab USA Inc
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Nalco Co LLC
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Priority to TW101101217A priority patent/TWI537250B/zh
Priority to KR1020137020525A priority patent/KR101853649B1/ko
Priority to JP2013552592A priority patent/JP5706973B2/ja
Priority to CN201280007432.4A priority patent/CN103339179B/zh
Priority to PCT/US2012/023453 priority patent/WO2012106410A2/en
Priority to EP12741845.7A priority patent/EP2670800B1/en
Priority to ES12741845.7T priority patent/ES2665976T3/es
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C7/00—Purification; Separation; Use of additives
    • C07C7/20—Use of additives, e.g. for stabilisation
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C253/00—Preparation of carboxylic acid nitriles
    • C07C253/32—Separation; Purification; Stabilisation; Use of additives
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/48—Separation; Purification; Stabilisation; Use of additives
    • C07C67/62—Use of additives, e.g. for stabilisation

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  • This invention relates to compositions of matter and methods of using them to inhibit unwanted polymerization reactions of ethylenically unsaturated monomers.
  • Polymerization inhibitors are known to be useful in preventing or reducing the unwanted polymerization of ethylenically unsaturated monomers which are handled at various stages of chemical processes in their manufacture and usage.
  • this invention illustrates a composition of inhibitors and retarders and its use in unwanted polymerization inhibition in handling the ethylenically unsaturated monomers.
  • Inhibitors prevent polymerization reactions from occurring. Inhibitors however are consumed rapidly. In cases of emergency when for mechanical or other reasons more inhibitor cannot be added, previously added inhibitor will be rapidly consumed and the unwanted polymerization reactions will then rapidly recur. Retarders slow down the rate of polymerization reactions but are not as effective as inhibitors. Retarders however are usually not consumed as quickly so they are more reliable in cases of emergency.
  • Ethylenically unsaturated monomers are reactive by their nature and they tend to polymerize through a radical polymerization mechanism. Unwanted polymerization reactions often impose operational concerns or difficulties while handling the ethylenically unsaturated monomers because the polymer formation may result in fouling and potential shutdown of operation equipment. Such is the case with the manufacture, transportation and storage of the monomers. It is especially a serious operational problem when distillation operation is involved in the manufacture and recovery of ethylenically unsaturated monomers, in which elevated operational temperatures accelerate the polymerization reactions of the monomers. Acrylonitrile is used as an example illustrating the handling of ethylenically unsaturated monomers, but not limited to, the manufacturing process described below.
  • the manufacture of acrylonitrile typically comprises three stages: the reaction, the recovery, and the purification stages.
  • the reaction stage propylene, oxygen or air and ammonia are fed to a fluidized catalytic reactor.
  • propylene undergoes a catalytic ammoxidation reaction to form acrylonitrile by reaction with ammonia and oxygen at an elevated temperature.
  • the resulting acrylonitrile-containing reactor effluent is then cooled down in an aqueous quench column. In the quench column, unreacted ammonia is removed as ammonium sulfate by neutralizing with sulfuric acid.
  • the quench column overhead acrylonitrile-containing effluent undergoes a water absorption process in an absorber column to capture acrylonitrile and to dispose volatile components in the stream. Then, the effluent proceeds to a recovery column in which acrylonitrile is recovered through the overhead of the recovery column as an azeotropic distillate with hydrogen cyanide and water. This overhead distillate is then passed on to the purification stage.
  • a Heads Column is used to recover hydrogen cyanide from the feed.
  • a Drying Column dehydrates the acrylonitrile.
  • a Product Column yields the acrylonitrile product.
  • hydrogen cyanide is separated as an overhead distillate through a conventional distillation operation.
  • the bottom of the Heads Column is sent to a decanter for water removal.
  • the organic phase of this decanter is routed to the Drying Column for further dehydration through an azeotropic distillation operation.
  • the Drying Column overhead distillate is recycled back to the Heads Column, and the Drying Column bottoms are delivered to Product Column.
  • heavy and light impurities are removed and a commercial grade of acrylonitrile is obtained as product.
  • heating and elevated temperatures are involved in the Heads, Drying and Product column operations.
  • acrylonitrile tends to polymerize, and the polymerization reaction intensifies at elevated temperatures. Polymerization of acrylonitrile is unwanted in acrylonitrile manufacture since the resulting polymer tends to precipitate out of process stream, depositing on process equipment surfaces, and impairs the operation of the equipment. Acrylonitrile polymerization related fouling is often an operational concern for manufacturing and processing acrylonitrile, and it is especially a serious problem in the recovery and purification stages in acrylonitrile manufacture. Polymerization inhibitors have to be used routinely by acrylonitrile producers to mitigate polymerization induced fouling in process equipment or to stabilize acrylonitrile during transportation and storage. Nitroxide stable free radicals and hydroquinone (HQ) have been used to address these polymerizations.
  • HQ hydroquinone
  • HQ by itself is a less than optimal solution for unwanted polymerizations.
  • HQ is only partially effective in inhibiting these polymerization reactions.
  • HQ is a toxic chemical with environmental concerns.
  • Nitroxide stable free radicals nitroxide hydroxylamines, N,N′-dialkyl/aryl substituted hydroxylamines, phenolic antioxidants, phenylenediamines and phenothiazines are well known reagents in the prevention of unwanted polymerization of ethylenically unsaturated monomers.
  • the use of nitroxide stable radicals as polymerization inhibitors for ethylenically unsaturated monomers is mentioned for example in U.S. Pat. No. 3,744,988 which discusses the use of nitroxides, such as HTMPO in the inhibition of unwanted polymerization and resultant fouling in acrylonitrile manufacture.
  • U.S. Pat. No. 4,670,131 discloses the use of stable free radicals, such as nitroxide, to inhibit polymerization of olefinic compounds.
  • Nitroxides are generally known as the most effective inhibitors owing to their superior inhibiting capability. Kinetically they are capable of scavenging carbon-centered free radicals at a nearly diffusion-controlled rate which is several orders of magnitude faster than phenolic compounds. However, their kinetic superiority is not always advantageous under certain circumstances.
  • One issue of concern is their fast consumption rate as inhibitors.
  • Other issues of concern are their consumption through non-inhibition, and their unwanted reactions with process stream components or other inhibitor additives.
  • high nitroxide inhibitor dosages are often required for a given inhibition efficacy thereby making their use economically unattractive or even infeasible. Even worse, their interference with other inhibitors often results in antagonism and outright ineffectiveness as inhibitors.
  • N-hydroxy substituted hindered amine such as 1,4-dihydroxy-2,2,6,6-tertamethylpiperidine
  • N-hydroxy substituted hindered amines are usually prepared by reducing the corresponding nitroxide stable free radicals with a reducing reagent.
  • N-hydroxy substituted hindered amines are excellent hydrogen donor due to the weak NO—H bond in the compounds, and thus they are efficient antioxidants. As antioxidants they react with peroxide radicals easily, while they are converted to their corresponding nitroxide.
  • each N-hydroxy substituted hindered amine is equivalent to one hydrogen donor and one nitroxide inhibitor when peroxyl radicals and carbon-centered radicals are co-present, which is an attractive incentive offered by N-hydroxy substituted hindered amines.
  • N-hydroxy substituted hindered amines are not stable when exposed to an oxygen-containing environment, such as storage in open air, as they are easily and gradually oxidized back to their corresponding nitroxide radicals.
  • 5,728,872 discloses a combination of a nitroxide stable free radical, such as HTMPO, with a dihetero-substituted benzene having at least one transferable hydrogen, such as MEHQ, in inhibiting the premature polymerization of acrylic acid during the distillation process, either with or without the presence of oxygen.
  • a nitroxide stable free radical such as HTMPO
  • MEHQ transferable hydrogen
  • U.S. Pat. No. 5,955,643 discusses the use of a combination of nitroxide and phenylenediamine to inhibit the premature polymerization of vinyl aromatic monomers, such as styrene.
  • 6,337,426 discusses a combination use of phenylenediamine and nitroxide to inhibit the premature polymerization of reactive light olefins, such as butadiene.
  • U.S. Pat. No. 6,447,649 teaches the combined use of nitroxides and aliphatic amines to inhibit premature polymerization of vinyl monomers under both process and storage conditions. Examples of aliphatic amines are ethylenediamine, butane-1,4-diamine and propylamine.
  • US Published Patent Application 2004/0132930 discusses the combined use of a nitroxide and a dialkylhydroxylamine as a short-stopper in an aqueous suspension polymerization of vinyl chloride or mixed with another vinyl monomer.
  • U.S. Pat. No. 5,322,960 discloses the combined use of a nitroxide, phenol and phenothiazine compounds in the inhibition of premature polymerization of (meth)acrylic acid and their esters.
  • U.S. Pat. No. 6,300,513 discloses the combined use of an N-oxyl compound, N-hydroxy-2,2,6,6-tetramethylpiperidine, and 2,2,6,6-tetramethylpiperidine to stabilize vinyl compounds during their transport and storage.
  • N-oxyl compounds are effective stabilizers for vinyl compounds, but they are lost with time in vinyl compounds.
  • the co-presence of all three in a vinyl compound significantly reduces the loss of N-oxyl compounds with time in the vinyl compound.
  • nitroxides can sometimes be combined with other inhibitors or retarders these combinations often suffer from compatibility and storage issues, and are only useful in a limited number of environmental conditions.
  • At least one embodiment of the invention is directed towards a method of inhibiting the unwanted polymerization of an ethylenically unsaturated monomer prone to polymerization.
  • the method comprises the steps of: a) providing a nitroxide stable free radical solution having a solvent, b) adding a sufficient amount of dialkyl/aryl hydroxylamine to the solution to reduce the nitroxide into the nitroxide hydroxylamine, c) adding to the solution a polymerization prevention component, thereby forming an inhibiting composition, and d) adding the composition to a fluid containing ethylenically unsaturated monomers.
  • the polymerization prevention component is one selected from the list consisting of phenolic antioxidants, phenylenediamine derivatives, phenothiazine derivatives, and any combination thereof.
  • the polymerization prevention component is targeted towards ethylenically unsaturated monomers.
  • the polymerization prevention component is an item that would otherwise react with the nitroxide stable free radical but for the conversion of the nitroxide into nitroxide hydroxylamine.
  • the nitroxide stable free radical may be a derivative of TMPO.
  • the dialkyl/aryl hydroxylamine may be a dialkyl hydroxylamine and may be DEHA.
  • the phenolic antioxidant may be HQ. If the antioxidant were to have reacted with the nitroxide at least one of the antioxidants or the nitroxides may have had a lower inhibiting capacity than if they were not so reacted.
  • the phenolic antioxidant may be one selected from the list consisting of: MEHQ, BHT, TBC and any combination thereof.
  • the phenylenediamine derivative may be one selected from the list consisting of phenylenediamine, N-substituted phenylenediamine, and N,N′-substituted phenylenediamine.
  • the phenothiazine derivative may be selected from phenothiazine and substituted phenothiazines.
  • the nitroxide stable free radical may be HTMPO
  • the dialkyl/aryl hydroxylamine may be DEHA
  • the phenolic antioxidant may be HQ.
  • the ethylenically unsaturated monomer may be selected from the list consisting of: acrylonitrile, (meth)acrolein, acrylic acid, methacrylic acid, acrylate esters, such as butylacrylate, ethylacrylate and methyl methacrylate, ethylene, propylene, styrene, divinylbenzene, butadiene, isoprene, vinylacetate, vinylacohol, and any combination thereof.
  • At least one embodiment of the invention is directed towards a composition for inhibiting the unwanted polymerization of an ethylenically unsaturated monomer prone to polymerization.
  • the composition is produced by: a) providing a nitroxide stable free radical solution having a solvent, b) adding a sufficient amount of dialkyl/aryl hydroxylamine to the solution to reduce the nitroxide into the nitroxide hydroxylamine, and c) adding to the solution a polymerization prevention component, thereby forming an inhibiting composition.
  • the polymerization prevention component is one selected from the list consisting of: phenolic antioxidants, phenylenediamine derivatives, phenothiazine derivatives, and any combination thereof.
  • the polymerization prevention component is targeted towards the ethylenically unsaturated monomer.
  • the polymerization prevention component is an item that would otherwise react with the nitroxide stable free radical but for the conversion of the nitroxide into nitroxide hydroxylamine.
  • FIG. 1 is a graph illustrating the effectiveness of the invention at inhibiting the polymerization of pure acrylonitrile.
  • FIG. 2 is a graph illustrating the effectiveness of the invention at inhibiting the polymerization of acrylonitrile in the presence of water, acetic acid, and air.
  • acrylate esters means the esterification products of (meth)acrylic acid.
  • BHT butylated hydroxytoluene
  • HQ hydroquinone
  • HTMPO means 4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxyl.
  • Induction time means the period of time in which in an ideal closed system a composition of matter completely prevents the formation of a particular polymer during a given reaction.
  • “Inhibitor” means a composition of matter that inhibits the formation of the particular polymer during an induction time but after the induction time has lapsed, the particular polymer's formation occurs at substantially the same rate that it would formed at in the absence of the composition of matter.
  • MEHQ means 4-methoxyphenol
  • (meth)acrolein means both acrolein and methacrolein
  • (meth)acrylic acid means both acrylic acid and methacrylic acid
  • PDA means phenylenediamine
  • PTZ means phenothiazine
  • Retarder means a composition of matter, which does not have an induction time, but instead once added to the given reaction the composition of matter reduces the rate at which the formation of the particular polymer occurs relative to the rate at which it would have formed in the absence of the composition of matter.
  • TBC means 4-tert-butyl catechol.
  • TMPO means 2,2,6,6-tetramethylpiperidinal-1-oxyl
  • an unwanted polymerization reaction of an ethylenically unsaturated monomer is prevented at the handling stage of the ethylenically unsaturated monomer by the presence of an effective amount of an inhibiting composition.
  • the composition comprises:
  • the nitroxide stable free radical is a derivative of TMPO.
  • HTMPO is an example of a TMPO derivative.
  • Other TMPO derivatives include, but are not limited to 4-oxo-TMPO, 4-amino-TMPO, 4-acetate-TMPO, Bis-(2,2,6,6-tetramethylpiperidine-1-oxyl)sebacate, and any combination thereof.
  • dialkyl/aryl hydroxylamine is a dialkyl or diaryl hydroxylamine.
  • examples are diethyl hydroxylamine (DEHA), dipropyl hydroxylamine, dibutyl hydroxylamine, bis-(hydroxypropyl)hydroxylamine (HPHA) and dibenzyl hydroxylamine.
  • the phenolic antioxidant is selected from hindered and nonhindered phenols targeted toward an ethylenically unsaturated monomer.
  • examples of such phenolic antioxidants are HQ, BHT, TBC, and MEHQ.
  • the phenylenediamine derivative is selected from an unsubstituted phenylenediamine, N-substituted phenylenediamine or N,N′-substituted phenylenediamine targeted towards an ethylenically unsaturated monomer, and any combination thereof.
  • phenylenediamine derivatives are 1,4-phenylenediamine, N,N′-dimethyl-p-phenylenediamine, N, N′-di-sec-butyl-p-phenylenediamine, N-phenyl-N′-dibutyl-p-phenylenediamine, N-phenyl-N′-(1,4-dimethylphenyl)-p-phenylenediamine, N-phenyl-N′-(1,3-dimethylbutyl)-p-phenylenediamine, and any combination thereof.
  • the phenothiazine derivative is selected from PTZ and substituted PTZ targeted toward an ethylenically unsaturated monomer.
  • substituted PTZ include alkylated PTZ.
  • the ethylenically unsaturated monomer is selected from the list of: acrylonitrile, (meth)acrolein, (meth)acrylic acid, acrylate ester, ethylene, propylene, styrene, divinylbenzene, butadiene, isoprene, vinyl acetate, vinyl alcohol and any combination thereof.
  • Butyl acrylate, ethyl acrylate, methyl methacrylate are the examples of acrylate ester.
  • the solvent of the nitroxide stable free radical solution is selected from the list consisting of, but not limited to: water, alcohol, ether, ketone, ester, glycol, aliphatic and aromatic hydrocarbons, ethylenically unsaturated monomers and any combination thereof.
  • the polymerization prevention component is HQ and the targeted ethylenically unsaturated monomer is acrylonitrile, (meth)acrolein or (meth)acrylic acid.
  • the polymerization prevention component is TBC and the ethylenically unsaturated monomer is butadiene, isoprene, styrene, divinylbenzene, and/or acrylonitrile.
  • the polymerization prevention component is PTZ and the ethylenically unsaturated monomer is (meth)acrylic acid or acrylate ester.
  • the polymerization prevention component is PDA and the ethylenically unsaturated monomer is butadiene, isoprene, acrylonitrile, styrene, divinylbenzene, (meth)acrylic acid, and/or acrylate ester.
  • the polymerization prevention component is BHT and the ethylenically unsaturated monomer is ethylene, propylene, styrene, divinylbenzene, and/or acrylonitrile.
  • the polymerization prevention component is MEHQ and the ethylenically unsaturated monomer is acrylonitrile or (meth)acrolein or (meth)acrylic acid or acrylate esters, such as butylacrylate, ethylacrylate, methylmethacrylate.
  • the nitroxide is HTMPO
  • the dialkyl hydroxylamine is DEHA
  • the polymerization prevention component is HQ
  • the ethylenically unsaturated monomer is acrylonitrile.
  • nitroxide group or the corresponding nitroxide hydroxylamines, dialkyl/aryl hydroxylamine or its corresponding nitrone and a component selected from phenolic antioxidant, phenylenediamine or phenothiazine targeted towards an ethylenically unsaturated monomer results in a synergistic combination that is more effective than merely the sum of their parts.
  • This synergistic combination involves the nitroxide group acting as an antipolymerant (an inhibitor of the polymerization of carbon centered radicals), nitroxide hydroxylamine as an antioxidant (an inhibitor of peroxyl radicals) and also an in situ source for nitroxide antipolymerant, the dialkyl/aryl hydroxylamine as an antioxidant, the nitrone as an antipolymerant or antioxidant and the phenolic antioxidant, phenylenediamine or phenothiazine targeted towards a given ethylenically unsaturated monomer as an inhibitor or retarder.
  • This synergistic combination provides not only a synergistic inhibition function mechanism (antioxidant vs. antipolymerant or inhibitor vs.
  • this composition is the ease of delivery of this inhibitor package into an ethylenically unsaturated monomer handling system. Pre-formulations of this composition avoid the need for on-site blending and the associated safety and environmental concerns. Such a multi component blend reduces the expenses associated with additional injection points for multiple products.
  • An example inhibitor composition was prepared. HTMPO was dissolved in a solvent consisting of water, ether, and glycol. DEHA was then added into the solution. A discoloration was observed as the reaction between HTMPO and DEHA progressed. At the end of this reaction, compositional analysis confirmed the conversion of HTMPO to HTMPO hydroxylamine and the formation of a nitrone from DEHA. HQ was then added and dissolved with stirring. This composition was ready for use as an inhibitor product.
  • the performance of the above generated inhibitor composition was evaluated using a laboratory scale continuous flow distillation column.
  • the column consisted of a three-neck flask representing the column sump and reboiler, an insertion assembly with perforated metal plates representing the distillation column tray section, and a condenser representing the overhead condenser to provide distillation reflux.
  • a feed pump provided the column feed, and an outlet purge pump maintained the liquid level in the sump. Heating was provided via a heating mantle to the flask contents.
  • acrylonitrile Commercial grade acrylonitrile was purchased from Sigma-Aldrich (99+% pure, inhibited with 35-45 ppm MEHQ). Uninhibited acrylonitrile was obtained by removing the MEHQ. Benzoyl peroxide (BPO) (Aldrich, 97%) was employed as the polymerization initiator for the experiments.
  • BPO Benzoyl peroxide
  • FIG. 1 shows that the inhibitor composition made in Example 1 effectively inhibits polymer formation in pure acrylonitrile with a significant dosage response while the two HQ treated runs show little inhibition.
  • FIG. 2 The data shown in FIG. 2 was collected using the same apparatus as in Example 2, except that acetic acid, water and air were introduced in the distillation column, to simulate the distillation operation in the Heads or Drying column of an industrial acrylonitrile manufacture process.
  • FIG. 2 shows that in the presence of water, acetic acid, and air the HQ retarded acrylonitrile polymerization, while the Example 1 composition inhibited the polymerization up to 40 minutes and is mostly effective after 85 minutes have elapsed.

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US13/020,487 US8691994B2 (en) 2011-02-03 2011-02-03 Multi-component polymerization inhibitors for ethylenically unsaturated monomers
TW101101217A TWI537250B (zh) 2011-02-03 2012-01-12 乙烯系不飽和單體之多組分聚合反應抑制劑
EP12741845.7A EP2670800B1 (en) 2011-02-03 2012-02-01 Multi-component polymerization inhibitors for ethylenically unsaturated monomers
JP2013552592A JP5706973B2 (ja) 2011-02-03 2012-02-01 エチレン性不飽和モノマの重合阻害方法、および、多成分重合阻害組成物
CN201280007432.4A CN103339179B (zh) 2011-02-03 2012-02-01 用于烯键式不饱和单体的多组分阻聚剂
PCT/US2012/023453 WO2012106410A2 (en) 2011-02-03 2012-02-01 Multi-component polymerization inhibitors for ethylenically unsaturated monomers
KR1020137020525A KR101853649B1 (ko) 2011-02-03 2012-02-01 에틸렌계 불포화 단량체용 다성분 중합 억제제
ES12741845.7T ES2665976T3 (es) 2011-02-03 2012-02-01 Inhibidores de polimerización multicomponentes para monómeros etilénicamente insaturados

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US20140316172A1 (en) * 2011-11-29 2014-10-23 Dorf Ketal Chemicals (India) Private Limited Amine Based Additive Composition for Control and Inhibition of Polymerization of Styrene, and Method of Use Thereof
US20150152053A1 (en) * 2013-12-03 2015-06-04 Ecolab USA, Inc. Nitroxide hydroxylamine and phenylenediamine combinations as polymerization inhibitors for ethylenically unsaturated monomer processes
US20180244605A1 (en) * 2017-02-27 2018-08-30 Ecolab Usa Inc. Anti-foulant formulation for compressors
US10731093B2 (en) 2014-11-26 2020-08-04 Borealis Ag Wash oil for use as an antifouling agent in gas compressors

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JP6043937B2 (ja) * 2012-08-16 2016-12-14 株式会社片山化学工業研究所 ビニル芳香族モノマーの重合を抑制するための組成物
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WO2018044644A1 (en) * 2016-08-31 2018-03-08 Ecolab USA, Inc. Method to inhibit polymerization in a process water
CN111100002B (zh) * 2018-10-25 2024-04-02 中国石油化工股份有限公司 一种复配型乙酸乙烯酯精馏阻聚剂及其使用方法
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JP2021004316A (ja) * 2019-06-26 2021-01-14 パナソニックＩｐマネジメント株式会社 樹脂組成物、プリプレグ、プリプレグの製造方法、積層板及びプリント配線板
KR102400224B1 (ko) * 2020-06-03 2022-05-23 주식회사 켐트로닉스 알킬 3-알콕시 프로피오네이트의 제조 방법
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TW202404930A (zh) * 2022-04-01 2024-02-01 美商藝康美國公司 在共軛二烯單體之萃取蒸餾期間減少非所要之乳化聚合
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